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DOI: 10.1055/s-0029-1218555
Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes with Arylamines
Publication History
Publication Date:
07 January 2010 (online)
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Abstract
A mixture of [P(t-Bu)2-o-biphenyl]AuCl and AgOTf catalyzes the intermolecular hydroamination of monosubstituted and 1,1- and 1,3-disubstituted allenes with primary and secondary arylamines.
Key words
allylations - allenes - amines - homogenous catalysis - regioselectivity
- Supporting Information for this article is available online:
- Supporting Information
- For recent reviews of catalytic hydroamination, see:
-
1a
Müller TE.Hultzsch KC.Yus M.Foubelo F.Tada M. Chem. Rev. 2008, 108: 3795 -
1b
Widenhoefer RA.Han X. Eur. J. Org. Chem. 2006, 4555 -
1c
Pohlki F.Doye S. Chem. Soc. Rev. 2003, 32: 104 -
1d
Hong S.Marks TJ. Acc. Chem. Res. 2004, 37: 673 - For recent examples of the intramolecular hydroamination of allenes, see:
-
2a
Volz F.Krause N. Org. Biomol. Chem. 2007, 5: 1519 -
2b
Morita N.Krause N. Eur. J. Org. Chem. 2006, 4634 -
2c
Morita N.Krause N. Org. Lett. 2004, 6: 4121 -
2d
Hoover JM.Petersen JR.Pikul JH.Johnson AR. Organometallics 2004, 23: 4614 -
2e
Zhang Z.Bender CF.Widenhoefer RA. Org. Lett. 2007, 9: 2887 -
2f
LaLonde RL.Sherry BD.Kang EJ.Toste FD. J. Am. Chem. Soc. 2007, 129: 2452 -
2g
Lee PH.Kim H.Lee K.Kim M.Noh K.Kim H.Seomoon D. Angew. Chem. Int. Ed. 2005, 44: 1840 -
2h
Patil NT.Lutete LM.Nishina N.Yamamoto Y. Tetrahedron Lett. 2006, 47: 4749 -
2i
Zhang Z.Bender CF.Widenhoefer RA. J. Am. Chem. Soc. 2007, 129: 14148 - 3
Zhang Z.Liu C.Kinder RE.Han X.Qian H.Widenhoefer RA. J. Am. Chem. Soc. 2006, 128: 9066 - 4
Walsh PJ.Baranger AM.Bergman RG. J. Am. Chem. Soc. 1992, 114: 1708 -
5a
Johnson JS.Bergman RG. J. Am. Chem. Soc. 2001, 123: 2923 -
5b
Ayinla RO.Schafer LL. Inorg. Chim. Acta 2006, 359: 3097 - 6
Al-Masum M.Meguro M.Yamamoto Y. Tetrahedron Lett. 1997, 38: 6071 - 7
Besson L.Gore J.Cazes B. Tetrahedron Lett. 1995, 36: 3857 - 8
Nishina N.Yamamoto Y. Angew. Chem. Int. Ed. 2006, 45: 3314 - 9
Nishina N.Yamamoto Y. Synlett 2007, 1767 - 10
Lavallo V.Frey GD.Donnadieu B.Soleilhavoup M.Bertrand G. Angew. Chem. Int. Ed. 2008, 47: 5224 - 11
Kinder RE.Zhang Z.Widenhoefer RA. Org. Lett. 2008, 10: 3157 - 12
Zeng X.Soleilhavoup M.Bertrand G. Org. Lett. 2009, 11: 3166 -
13a
Lavallo V.Frey GD.Kousar S.Donnadieu B.Bertrand G. Proc. Natl. Acad. Sci. U.S.A. 2007, 104: 13569 -
13b
Frey GD.Dewhurst RD.Kousar S.Donnadieu B.Bertrand G. J. Organomet. Chem. 2008, 693: 1674 - 15
Zhang Z.Widenhoefer RA. Org. Lett. 2008, 10: 2079
References and Notes
Experimental Procedure and Spectroscopic Data for the Gold(I)-Catalyzed Hydroamination of 1 with o -Bromo-aniline (Table 2, entry 2): Dioxane (0.50 mL) was added to a mixture of o-bromoaniline (39 mg, 0.23 mmol), (3)AuCl (6.2 mg, 1.1 × 10-² mmol), and AgOTf (2.8 mg, 1.1 × 10-² mmol) and the resulting suspension was stirred for 10 min at r.t. 3-Methyl-1,2-butadiene (1; 29 mg, 0.43 mmol) was added via syringe and the resulting mixture was stirred at 45 ˚C for 24 h. Column chromatography of the reaction mixture (SiO2; hexanes-EtOAc, 15:1) gave N-(3-methyl-2-butenyl)-o-bromoaniline (48 mg, 87%) as a pale yellow oil. ¹H NMR (400 MHz, CDCl3): δ = 7.41 (dd, J = 1.5, 8.5 Hz, 1 H), 7.17 (dd, J = 1.5, 7.8 Hz, 1 H), 6.62 (dd, J = 1.0, 8.3 Hz, 1 H), 6.55 (dt, J = 1.5, 7.5 Hz, 1 H), 5.31-5.35 (m, 1 H), 4.23 (br s, 1 H), 3.72 (d, J = 6.8 Hz, 2 H), 1.76 (d, J = 1.0 Hz, 3 H), 1.72 (s, 3 H). ¹³C{¹H} NMR (100 MHz, CDCl3): δ = 145.1, 136.1, 132.3, 128.4, 121.1, 117.5, 111.4, 109.7, 41.9, 25.7, 18.1. HRMS: m/z [M+] calcd for C11H14BrN: 239.0310; found: 239.0313.